EP0008492A1 - Verfahren zur Herstellung eines aromatischen Polyester-Polycarbonats - Google Patents

Verfahren zur Herstellung eines aromatischen Polyester-Polycarbonats Download PDF

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Publication number
EP0008492A1
EP0008492A1 EP79301335A EP79301335A EP0008492A1 EP 0008492 A1 EP0008492 A1 EP 0008492A1 EP 79301335 A EP79301335 A EP 79301335A EP 79301335 A EP79301335 A EP 79301335A EP 0008492 A1 EP0008492 A1 EP 0008492A1
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EP
European Patent Office
Prior art keywords
dihydroxy
diaryl
compound
solution
terephthaloyl chloride
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP79301335A
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English (en)
French (fr)
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EP0008492B1 (de
Inventor
Mori Hajime
Kohyama Katsuhisa
Nakamura 1403-70 Aza-Haranoshita Katsuhiko
Sakata Katsuyuki
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Mitsubishi Kasei Corp
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Mitsubishi Kasei Corp
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Publication of EP0008492A1 publication Critical patent/EP0008492A1/de
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur

Definitions

  • This invention relates to a method for the manufacture of an aromatic polyester-polycarbonate. More particularly, this invention relates to an advantageous method for commercially manufacturing an aromatic polyester-polycarbonate which possesses excellent mechanical properties, thermal stability chemical resistance and transparency.
  • aromatic polyester-polycarbonates have been prepared by reacting 2,2-bis-(4-hydroxyphenyl)-propane(bis-phenol A) or similar compound with a terephthaloyl chloride compound. It has been suggested that the starting materials should be reacted in a homogeneous system in an organic solvent containing pyridine and then allowing the resultant reaction mixture to undergo polycondensation with phosgene (Japanese Patent Laid-open Publication No. 128992/1977 and Goldberg, U.S. Patents 3,030,331 and 3,169,121). By this technique an aromatic polyester-polycarbonate can be obtained which has excellent properties.
  • one object of the present invention is to provide a method of synthesizing an aromatic polyester-polycarbonate which does not entail the use of pyridine as an acid acceptor.
  • Suitable dihydroxy-diaryl compounds which can be used in the present invention include compounds of the formula: wherein, X is a divalent group such as -0-, -S-, -SO- or -S02-, and both R groups are the same or different and are a hydrogen atom , a monovalent hydrocarbon radical or a halogen atom, and R' is a divalent hydrocarbon radical.
  • dihydroxy-diaryl compounds include bis-(hydroxy-aryl)-alkanes such as bis-(4-hydroxyphenyl)-methane, 1,1-bis-(4-hydroxyphenyl)-ethane, 2,2-bis-(4-hydroxyphenyl)-propane, 2,2-bis-(4-hydroxyphenyl)-butane, 2,2-bis-(4-hydroxyphenyl)-octane, bis-(4-hydroxyphenyl)-alkaline solution with a terephthaloyl chloride in an organic-solvent solution to produce a low molecular polyester oligomer possessing a terminal-OH group.
  • hydroxy-aryl)-alkanes such as bis-(4-hydroxyphenyl)-methane, 1,1-bis-(4-hydroxyphenyl)-ethane, 2,2-bis-(4-hydroxyphenyl)-propane, 2,2-bis-(4-hydroxyphenyl)-butane, 2,2-bis-(4
  • phosgene is reacted with the low molecular polyester oligomer obtained in the first stage to produce a low molecular polyester oligomer possessing a terminal-OCOCl group.
  • an organic-solvent solution of the low molecular weight polyester oligomer obtained in the second state is subjected to polycondensation with an aqueous alkaline solution of a dihydroxy-diaryl compound to form the desired product.
  • Suitable dihydroxy-diaryl compounds which can be used in the present invention include compounds of the formula: wherein, X is a divalent group such as -0-, -S-, -SO- or -S0 2 -, and both R groups are the same or different and are a hydrogen atom , a monovalent hydrocarbon radical or a halogen atom, and R' is a divalent .hydrocarbon radical.
  • dihydroxy-diaryl compounds include bis-(hydroxy-aryl)-alkanes such as bis-(4-hydroxypheny1)-methane, 1,1-bis-(4-hydroxyphenyl)-ethane, 2,2-bis-(4-hydroxyphenyl)-propane, 2,2-bis-(4-hydroxyphenyl)-butane, 2,2-bis-(4-hydroxyphenyl)-octane, bis-(4-hydroxyphenyl)--phenyl-methane, 2,2-bis-(4-hydroxy-3-methylphenyl)-propane, 1,1-bis-(4-hydroxy-3-tert.
  • hydroxy-aryl)-alkanes such as bis-(4-hydroxypheny1)-methane, 1,1-bis-(4-hydroxyphenyl)-ethane, 2,2-bis-(4-hydroxyphenyl)-propane, 2,2-bis-(4-hydroxyphenyl)-butane, 2,2-bis-(4-hydroxypheny
  • butylphenyl)-propane 2,2-bis-(4-hydroxy-3-bromophenyl)-propane, 2,2-bis-(4-hydroxy-3,5-dibromophenyl)-propane and 2,2-bis-(4-hydroxy--3,5-dichlorophenyl)-propane; bis-(hydroxyaryl)-cyclo-alkanes such as 1,1-bis-(4-hydroxyphenyl)-cyclo-pentane and 1,1-bis-(4-hydroxyphenyl)-cyclo-hexane; dihydroxy-diaryl ethers such as 4,4'-dihydroxy-diphenyl ether and 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether; dihydroxy-diaryl sulfides such as 4,4'-dihydroxy diphenyl sulfide and 4,4'-dihydroxy -3,3'-dimethyldiphenyl sulfide; dihydroxy
  • Suitable alkalis which can be advantageously employed in the preparation of the aqueous alkaline solution of the dihydroxy-diaryl compound mentioned above include caustic alkalis such as sodium hydroxide, potassium hydroxide, and lithium hydroxide. From the commercial point of view, however, it is advantageous to use sodium hydroxide.
  • terephthaloyl chloride reactant of the present process those terephthaloyl chloride compounds which contain a halogen atom or an alkyl group in their ring structure may be employed.
  • Suitable terephthaloyl chlorides include 2,4-dichloro-terephthaloyl chloride, 2,5-dibromoterephthaloyl chloride, chloro-terephthaloyl chloride, methyl-terephthaloyl chloride and 2,5-dimethyl-terephthaloyl chloride besides terephthaloyl chloride.
  • the terephthaloyl chloride reactant may be dissolved in any organic solvent which is insoluble in water.
  • Suitable organic solvents which are useful include chlorinated hydrocarbons such as methylene chloride, chloroform, dichloroethane, trichloroethane, tetrachloroethane, 1,2-dichloroethylene and dichlorobenzene.
  • chlorinated hydrocarbons such as methylene chloride, chloroform, dichloroethane, trichloroethane, tetrachloroethane, 1,2-dichloroethylene and dichlorobenzene.
  • organic solvents such as dioxane, tetrahydrofuran, acetophenone, toluene, xylene, cyclohexane, acetone and n-heptane are also satisfactory as a solvent medium.
  • methylene chloride is a choice solvent.
  • an aqueous alkaline solution of a suitable dihydroxy-diaryl compound and an organic-solvent solution of a terephthaloyl chloride are mixed to prepare an ester.
  • the concentration of the dihydroxy-diaryl compound in the aqueous alkaline solution is not critical and can be widely varied, it is desirable to select a concentration in the neighborhood of the point of saturation because the amount of materials employed in the reaction can be minimized which is very desirable from the standpoint of industrial operations.
  • the concentration of the terephthaloyl chloride varies with the kind of solvent being used. When methylene chloride is used as the solvent, for example, it is desirable to vary the concentration in the range of from 1% by weight to the point of saturation, preferably from 2 to 10 by weight.
  • the mixing ratio of the dihydroxy-diaryl compound relative to the terephthaloyl chloride compound should be such that the dihydroxy-diaryl compound is present in excess amount relative to the terephthaloyl chloride compound.
  • This mixing ratio is desirably selected within the range of 1:0.5-0.75, preferably 1:0.6-0.7.
  • the esterification reaction is preferably conducted over a short period of time.
  • the esterification reaction may be continued with thorough agitation for a period of from five seconds to two minutes, preferably from five seconds to 30 seconds.
  • the residence time of the reactants in the reaction vessel is too long, it is possible that the terephthaloyl chloride will undergo hydrolysis or an oligomer of undesirably high molecular weight may be produced. It is, therefore, desirable to maintain suitable control of the reaction time, for instance, by using a mixer such as a packed column, orifice column, multistage column or hollow tube.
  • reaction temperature and the reaction pressure are not especially critical. Those conditions generally used for interfacial polymerization are quite satisfactory.
  • the reaction mixture which is obtained from the first stage esterification reaction is an organic solvent-water type emulsion containing therein a polyester oligomer having a terminal-OH group and a by-product alkali metal chloride.
  • phosgene is reacted with the ester product in the first stage reaction mixture to effect conversion of the terminal-OH group into a -OCOC1 group.
  • the amount of phosgene which is employed in the second stage reaction is such that the combined amount of phosgene and the terephthaloyl chloride compound used in the second stage amounts to a proportion of 1 to 3, preferably 1.25 to 2, based on a unit amount of the dihydroxy-diaryl compound used in the first stage, (molar ratio). If the amount of phosgene employed is too small, the extent of conversion of the terminal-OH group of the oligomer to the -OCCCl group is not as great as is required.
  • the reaction in the second stage is carried out over a sufficiently short period of time. Desirably, the reaction is continued with thorough agitation over a period of from five seconds to two minutes, preferably from five seconds to 30 seconds. Again in the second stage, if the residence time is too long, there is a possibility that the terminal-OH group of the low molecular polyester oligomer produced in the first stage will bind with the chloroformate terminal to produce a high molecular weight oligomer.
  • the reaction mixture which results from the phosgenation reaction is a mixture of an organic-solvent solution of the polyester oligomer possessing a terminal-OC0Cl group and an aqueous solution containing large amounts of a by product alkali metal chloride.
  • a dihydroxy- diaryl compound in an aqueous alkaline solution is reacted in a polycondensation reaction with the reaction mixture from the second stage.
  • the reaction mixture from the second stage may be used in its unmodified form in the third stage. Otherwise, this reaction mixture may be freed from the water phase containing the by-product alkali metal chloride before it is transferred to the third stage.
  • the dihydroxy-diaryl compound used in the third stage may be similar to or dissimilar to that used in the first stage.
  • the amount of the dihydroxy- diaryl compound used is desirably not less than one equivalent per equivalent of terminal-OCOC1 groups in the polyester oligomer obtained from the second stage, and preferably is an amount within the ranee of from 1.1 to 2 times the amount of polyester oligomer on an equivalent weight basis.
  • the amount of dihydroxy-diaryl compound employed is less than an equivalent relative to the polyester oligomer, the polycondensation reaction does not proceed sufficiently.
  • the amount of the dihydroxy-diaryl compound employed is too large, although the reaction itself is not obstructed, the amount of the unreacted dihydroxy-diaryl compound increases to such a level that additional process steps are necessary to remove the excess compound. This is a significant industrial disadvantage because additional expenses are incurred in the removal process.
  • amines which can be advantageously employed for this purpose include aliphatic tertiary amines such as trimethyl amine, triethyl amine, tri-n-propyl amine and tri-n-butyl amine.
  • Tne addition of the polymerization catalyst to the reaction solution may be made at any time prior to the start of the polycondensation reaction.
  • the addition of the polymerization catalyst, during or before the second stage is particularly advantageous, because the catalyst facilities phase separa tion which occurs subsequent to the second stage for the purpose of removing the aqueous phase.
  • a molecular weight-control ing agent such as phenol, p-tertiary butyl phenol or 2s6-dimethyl phenol can be added to the reaction solution.
  • the particular agent selected depends on the degree of polymerization which the polymer under production is desired to possess.
  • the molecular weight controlling agent can also be added during or before the second stage of the process without incurring any adverse effects.
  • the polycondensation reaction of the third stage must be conducted under agitated solution conditions for a period of from 30 minutes to several hours.
  • An agitation tank is quite satisfactory as a reaction vessel for this reaction.
  • reaction temperature and the reaction pressure in the third stage are not critical. In fact, the reaction conditions generally used for the purpose of interfacial polymerization can be employed in the third stage.
  • the reaction mixture produced in the polycondensation reaction consists of an organic-solvent solution containing the desired aromatic polyester-polycarbonate product and an aqueous solution containing substantial amounts of by-product alkali metal chloride.
  • the reaction mixture can be purified by a series of washing steps involving the use of water, followed by washing with an aqueous acidic solution and finally washing with water in the order mentioned.
  • the aromatic polyester-polycarbonate product can be separated from the organic solvent by distillation of the solvent, by the addition of a product insoluble, reaction solvent soluble solvent to the mixture or by some other conventional technique.
  • an aromatic polyester-polycarbonate possessing excellent properties including mechanical properties, therma stability, chemical resistance and transparency and possessing a dihydroxy- diaryl compound residue:terephthalic acid residue:carbonate moiety molar ratio of 1:0.33-0.75:0.67-0.25, a glass transition point (Tg) of 165 to 195°C. and a terminal carboxyl group content of less than 10 eq/10 g of polymer can be obtained.
  • Tg glass transition point
  • Tg glass transition point
  • the molar ratio for a composition is determined from the ratio of the peak at 1,740 cm -1 in the infrared spectrum for the -C00- group and the peak at 1,770 cm -1 for the -OC00- group.
  • a methylene chloride solution of terephthaloyl chloride and an aqueous alkaline solution of bis-phenol A at flow rates of 42.0 kg/hr. and 16.2 kg/hr. respectively were fed upwardly through the bottom of a vertical column having an inside diameter of 30 mm, a length of 1.5 m and filled with glass beads 5 mm in diameter.
  • the vertical column was enveloped with a jacket through which cold water at about 20°C was circulated.
  • phosgene was fed at a flow rate of 0.95 kg/hr. The reaction was continued for about one hour.
  • the reaction solution obtained was allowed to stand for about ten minutes over which time period the solution separated into a water phase and a methylene chloride phase.
  • the water phase had a pH of 13. Analysis ailed to detect any free terephthalic acid in the water phase.
  • the methylene chloride phase containing the polymer was washed first with water, then with an acid and again with water by an ordinary technique. Solvent'methylene chloride was evaporated from the washed methylene chloride phase and the resultant polymer mass was dried to afford a white solid polymer.
  • This polymer was found to possess an intrinsic viscosity [n] of 0.81 and a glass transition point (Tg) of 182°C.
  • the polymer was of a structure: bis-phenol A residue:terephthalic acid residue:carbonate moiety mole ratio of 2.0:0.77:1.23.
  • Example 2 In the same apparatus as used in Example 1, the same methylene chloride solution of a terephthaloyl chloride and the same aqueous bis-phenol A alkaline solution used above were fed upwardly through the column of Example at respective flow rates of 44.2 kg/hr. and 15.9 kg/hr. An aqueous 2% triethylamine solution was also fed upwardly through the bottom of the column at a flow rate of 0.2 kg/hr. When the reaction reached its stationary state, the supply of phosgene through the branched tube disposed about the middle of the column was started at a flow rate of 0.75 kg/hr. Phosgenation was continued for about one hour. The resultant reaction solution immediately separated into a water phase and a methylene chloride phase after the reaction solution was placed in a receptacle. The water phase had a pH of 13. Analysis detected no free terephthalic acid in the water phase.
  • the viscosity of the reaction solution increased in about five minutes and remained substantially constant thereafter. In spite of increases in viscosity, agitation was continued for one hour. The reaction ranged from 26 to 29°C.
  • This polymer was found to have an intrinsic viscosity [n] of 0.70 and a glass transition point (Tg) of 172°C.
  • the polymer was of a structure: bis--phenol A residue:terephthalic acid residue:carbonate moiety mole ratio of 2.0:0.91:1.09.
  • the methylene chloride solution of terephthaloyl chloride and the aqueous alkaline solution of bis-phenol A were fed at respective rates of 31.2 kg/hr. and 11.7 kg/hr. through a stainless steel tube 20 m long and having a 4 mm inside diameter.
  • Phosgene was admitted into the reactor at a flow rate of 0.52 kg/hr. through a tube having an inside diameter of 3 mm disposed at a distance of 8 m from the inlet of the reactor.
  • the reaction solution flowing from the reactor immediately separated into two phases after it was deposited into a receptacle.
  • Example 2 A 250-ml portion of the methylene chloride phase which separated from the water phase was subjected to polycondensation and washing by faithfully following the procedure of Example 1, to afford a white solid polymer.
  • This polymer was found to possess an intrinsic viscosity [ ⁇ ] of 0.76 and a glass transition point (Tg) of 181°C.
  • the polymer was of a structure: bis-phenol A residue:terephthalic acid residue:carbonate moiety mole ratio of 2.0:1.14:0.86.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
EP79301335A 1978-08-10 1979-07-25 Verfahren zur Herstellung eines aromatischen Polyester-Polycarbonats Expired EP0008492B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP9759278A JPS5525427A (en) 1978-08-10 1978-08-10 Preparation of aromatic polyester-polycarbonate
JP97592/78 1978-08-10

Publications (2)

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EP0008492A1 true EP0008492A1 (de) 1980-03-05
EP0008492B1 EP0008492B1 (de) 1983-05-18

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EP79301335A Expired EP0008492B1 (de) 1978-08-10 1979-07-25 Verfahren zur Herstellung eines aromatischen Polyester-Polycarbonats

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US (1) US4252939A (de)
EP (1) EP0008492B1 (de)
JP (1) JPS5525427A (de)
CA (1) CA1127795A (de)
DE (1) DE2965435D1 (de)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2514012A1 (fr) * 1981-10-05 1983-04-08 Idemitsu Kosan Co Procede de preparation de polyesterpolycarbonates
EP0095022A2 (de) * 1982-04-02 1983-11-30 Allied Corporation Grenzflächenverfahren zur Herstellung von Phenolphthalein enthaltendem Poly(estercarbonat)
EP0095670A2 (de) * 1982-05-27 1983-12-07 Mitsubishi Kasei Corporation Verfahren zur Herstellung von aromatischen Polyesterpolycarbonatteilchen
EP0337207A2 (de) * 1988-04-12 1989-10-18 Bayer Ag Verfahren zur Herstellung von aromatischen Polycarbonaten, aromatischen Polyestercarbonaten und aromatischen Polyestern
EP0346761A2 (de) * 1988-06-11 1989-12-20 Bayer Ag Verfahren zur Herstellung von aromatischen Polycarbonaten

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5796017A (en) * 1980-12-04 1982-06-15 Mitsubishi Gas Chem Co Inc Production of aromatic polyester copolymer
JPS57174318A (en) * 1981-04-21 1982-10-27 Mitsubishi Chem Ind Ltd Production of aromatic polyester polycarbonate
US4395534A (en) * 1981-11-17 1983-07-26 Mitsubishi Gas Chemical Company, Inc. Process for producing aromatic polyester carbonate resin
US4431761A (en) * 1982-10-08 1984-02-14 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Ethynyl and substituted ethynyl-terminated polysulfones
US4499257A (en) * 1983-04-18 1985-02-12 Union Carbide Corporation Poly(ester-carbonate)s
DE3346945A1 (de) * 1983-12-24 1985-07-04 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von aromatischen polyestercarbonaten
US4939230A (en) * 1988-11-16 1990-07-03 The Dow Chemical Company Elimination of monocarbonate from polycarbonate
US5614599A (en) * 1994-10-31 1997-03-25 The Dow Chemical Company Stilbene-based polyester and polycarbonate compositions
CN114891199B (zh) * 2022-05-13 2024-06-25 西安交通大学 一种具有高介电常数的聚氟苯酯聚合物的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3110698A (en) * 1959-03-12 1963-11-12 Eastman Kodak Co Polyesters of carbonyldichlorides and process for polymerization and dope making
GB1139413A (en) * 1965-02-03 1969-01-08 Ici Fibres Ltd Polyester/polycarbonate block copolymers
FR2346386A1 (fr) * 1976-04-02 1977-10-28 Allied Chem Copolymeres bisphenol a terephtalate carbonate pouvant etre traites a l'etat de masse fondue

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE570531A (de) * 1957-08-22

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3110698A (en) * 1959-03-12 1963-11-12 Eastman Kodak Co Polyesters of carbonyldichlorides and process for polymerization and dope making
GB1139413A (en) * 1965-02-03 1969-01-08 Ici Fibres Ltd Polyester/polycarbonate block copolymers
FR2346386A1 (fr) * 1976-04-02 1977-10-28 Allied Chem Copolymeres bisphenol a terephtalate carbonate pouvant etre traites a l'etat de masse fondue

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2514012A1 (fr) * 1981-10-05 1983-04-08 Idemitsu Kosan Co Procede de preparation de polyesterpolycarbonates
EP0095022A2 (de) * 1982-04-02 1983-11-30 Allied Corporation Grenzflächenverfahren zur Herstellung von Phenolphthalein enthaltendem Poly(estercarbonat)
EP0095022A3 (en) * 1982-04-02 1984-02-01 Allied Corporation Interfacial process for producing poly(ester-carbonate) containing phenolphthalein
EP0095670A2 (de) * 1982-05-27 1983-12-07 Mitsubishi Kasei Corporation Verfahren zur Herstellung von aromatischen Polyesterpolycarbonatteilchen
EP0095670A3 (en) * 1982-05-27 1984-01-11 Mitsubishi Chemical Industries Limited Process for producing aromatic polyester polycarbonate particles
EP0337207A2 (de) * 1988-04-12 1989-10-18 Bayer Ag Verfahren zur Herstellung von aromatischen Polycarbonaten, aromatischen Polyestercarbonaten und aromatischen Polyestern
EP0337207A3 (de) * 1988-04-12 1989-12-13 Bayer Ag Verfahren zur Herstellung von aromatischen Polycarbonaten, aromatischen Polyestercarbonaten und aromatischen Polyestern
EP0346761A2 (de) * 1988-06-11 1989-12-20 Bayer Ag Verfahren zur Herstellung von aromatischen Polycarbonaten
EP0346761A3 (de) * 1988-06-11 1991-11-06 Bayer Ag Verfahren zur Herstellung von aromatischen Polycarbonaten

Also Published As

Publication number Publication date
CA1127795A (en) 1982-07-13
JPS5525427A (en) 1980-02-23
DE2965435D1 (en) 1983-07-07
JPS6240371B2 (de) 1987-08-27
EP0008492B1 (de) 1983-05-18
US4252939A (en) 1981-02-24

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